Triazine-Intercalated Metal Phosphates, Compositions, and Methods

ABSTRACT

The present invention relates to triazine-intercalated metal phosphates including at least one monomer unit of the following general formula (I): 
       (A-H) a   (+) [M b   m+ (H 2 PO 4 ) x1   (−) (HPO 4 ) x2   2(−) (PO 4 ) x3   3(−) (PO 3 ) y   (−) ] (a−) *pH 2 O  (I)
 
     The invention further relates to the use thereof, the specific compounds of the general formula (1), to the preparation thereof, and to compositions.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 13/818,672, filed May 8, 2013, which is a U.S. national phaseapplication of PCT Application No. PCT/EP2011/063567, filed Aug. 5,2011, which claims foreign priority to German Patent Application No.102010035103.2, filed Aug. 23, 2010. The contents of U.S. patentapplication Ser. No. 13/818,672, PCT Application No. PCT/EP2011/063567,and German Patent Application No. 102010035103.2 are incorporated hereinby reference.

The present invention relates to flame retardant compositions comprisingtriazine-intercalated metal phosphates with open framework structures,to the use thereof, to such metal phosphates and to the preparationthereof.

It is known that organophilic sheet silicates which have been produced,for example, by means of ion exchange can be used as filler materialsfor thermoplastic materials and for thermosets to obtain nanocomposites.In the case of use of suitable organophilic sheet silicates as fillermaterials, the physical and mechanical properties of the moldingsproduced in such a way are considerably improved. Of particular interestis the increase in the stiffness with at least equal toughness.Particularly good properties are exhibited by nanocomposites whichcomprise the sheet silicate in exfoliated form. These nanocomposites arepreferably used as flame retardants or as synergists.

WO-A 00/44669 discloses organophilic sheet silicates which are preparedby treatment of a natural or synthetic sheet silicate or of a mixture ofsuch silicates with a salt of an optionally quaternary cyclic melaminecompound or a mixture of such salts.

Similar considerations should also apply to organophilic metalphosphates with open framework structures (see definition in “A Reviewof Open Framework Structures”, Annu. Rev. Mater. Sci. 1996, 26,135-151), especially to those intercalated with melamine (intercalatesalso called inclusion compounds; see definition in ROMPP, Chemielexikon,9th ed., 1995, G. Thieme, Vol. 3, p. 2005).

The literature describes various melamine phosphates which do not haveopen framework structures, for instance melamine orthophosphate in Magn.Reson. Chem. 2007, 45, p. 231-246., bismelamine di(pyro)phosphate in J.Phys. Chem. B 2004, 108, 15069-15076 and melamine polyphosphate in J.Phys. Chem. B 2005, 109, 13529-13537. The use thereof as flameretardants is mentioned therein in the secondary literature cited.

Certain melamine metal phosphates are described in WO-A 2009/015772.However, these compounds possess, as shown by the aluminum compound,only limited intrinsic (thermal) stability which is insufficient forincorporation into polyamides (see examples 7 and 8).

Melamine-intercalated (layered) zirconium phosphates are known fromSolid State Sciences 2009, 11, 1007-1015. However, use as polymeradditives, especially as flame retardants, is not described therein.Other melamine-intercalated layered (metal) phosphates are notdocumented in the literature.

Intercalation of α,ω-alkanediamines into (layered) aluminum triphosphateis published in J. Inclusion Phenomena and Macrocyclic Chem. 1999, 34401-412.

The layer structure of aluminum triphosphate is documented in Chem.Commun. 2006, 747-749. An open network structure is known forethylenediamine-zinc phosphate adducts from Zeolites and RelatedMicroporous Materials 1994, 2229-2236.

Ethylenediaminebis(zinc phosphate) is claimed in U.S. Pat. No. 5,994,435and U.S. Pat. No. 6,207,735 as a flame retardant. JP 8269230 describesamine-zinc phosphates which also include the anions HPO₄, H₂PO₄,Zn₂(HPO₄)₃ and Zn₄[PO₄)₂ (HPO₄)₂]. Applications JP9040686, JP 10259275,JP11152373, JP11199708, JP11246754, JP11269187, JP11293155,JP2000063562, JP2000063563, JP2000154283, JP2000154287, JP2000154324 andJP2001031408 describe processes for preparing specific embodiments andcombinations of ethylenediamine-zinc phosphate. However, the processesare uneconomic since they either work with an H₃PO₄ excess or proceedfrom Zn(en)₃ complexes. JP9169784 and JP2001011462 publishdiethylenetriamine or piperazine-zinc phosphate complexes as flameretardants.

Inorganic phosphates with open framework structures are described in anarticle in Angew. Chem. 1999, 111, 3466-3492.

Disadvantages of the prior art compounds mentioned are the limitedintrinsic (thermal) stability and the unfavorable mechanical propertieswhich result after incorporation into the polymer substrate.

It is an object of the present invention to provide flame retardantcompositions which have a high degree of intrinsic (thermal) stabilityand impart outstanding mechanical properties to the polymer afterincorporation.

The object was achieved, inter alia, by the provision of flame retardantcompositions comprising

-   -   (a) at least one triazine-intercalated metal phosphate with at        least one monomer unit of the following general formula (I):

(A-H)_(a) ⁽⁺⁾[M_(b) ^(m+)(H₂PO₄)_(xi) ⁽⁻⁾(HPO₄)_(X2) ²⁽⁻⁾(PO₄)_(X3)³⁽⁻⁾(PO₃)_(y) ⁽⁻⁾]^((a−))*pH₂O  (I)

-   -   -   where        -   (A-H)⁽⁺⁾ is a triazine derivative of the formula (II-1),            (II-2) or (II-3)

-   -   -   each M is independently Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO,            ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce or Sn;        -   a is 1 to 6,        -   b is 1 to 14,        -   m=1 to 4,        -   x₁, x₂, x₃, y=0 to 12, where at least one of the variables            x₁, x₂, x₃>0 and p=0 to 5,        -   where: a+mb=x₁+2x₂+3x₃+y        -   and

    -   (b) at least one further flame retardant component other than        (a).

In a preferred embodiment of the invention, the flame retardantcompositions comprising the triazine-intercalated metal phosphates (a)of the formula (I) have open framework structures. The triazinederivatives, and likewise melon, are known as chemical precursors forcarbon nitride (C₃N₄)_(x).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts an example of a lattice section from an intercalationmodel of one embodiment of a compound.

FIG. 2 depicts the quantitative ³¹P NMR spectrum of the bismelaminealuminotriphosphate of Example 2.

FIG. 3 depicts the ³¹P NMR spectrum of the bismelamine zincodiphosphateof Example 5.

FIG. 4 depicts the ²⁷Al NMR spectrum of the bismelaminealuminotriphosphate of Example 2.

Triazine-intercalated metal phosphates, especially with open frameworkstructures which are preferably prepared by direct reaction of (aqueous)acidic metal phosphates with melamine and subsequent pretreatment fromthe corresponding precursors, exhibit high thermal stability inprocessing combined with excellent dispersing action and interfacialadhesion. These systems feature surprisingly good layer separation,combined with excellent adhesion to a multitude of polymers and fillers.It is additionally surprising that the inventive triazine-intercalatedmetal phosphates with open framework structures are not only outstandingfillers for improving the mechanical properties of polymers, but alsoact as flame retardants. The triazine-intercalated (metal) phosphateswith open framework structures may also consist of chain (ribbon)phosphates (catena type), sheet phosphates (ladder or phyllo type—allwith 1-D structures), layered phosphates (with 2-D structures) or 3-Dphosphates (zeolite type).

In a particularly preferred embodiment of the present invention, in theflame retardant compositions comprising component (a), (A-H)⁽⁺⁾=(II-1)and M=Zn or Al.

Preferably, component (b) is at least one metal compound, which is not ametal phosphate of component (a), or/and at least one metal-freephosphorus compound.

This at least one metal compound (b) is preferably a metal oxide, ametal hydroxide, a metal phosphate, a metal pyrophosphate, ahydrotalcite, a cationically or anionically modified organoclay, astannate or molybdate salt, a metal borate or metal phosphinate of theformula (III):

where R¹ and R² are each hydrogen or a straight-chain or branchedC₁-C₆-alkyl radical or a phenyl radical; and Mt=Ca, Mg, Zn or Al and m=2or 3, or a hypophosphite salt of the formula M^(m+)[H₂PO₂]_(m) ^(m−)(M=Al, Ca, Mg and Zn, and m=2 or 3).

Organoclays are understood to mean organophilieally modified clayminerals (principally montmorillonite) based on cation exchange, such astriethanol-tallow-ammonium montmorillonite andtriethanol-tallow-ammonium hectorite (Dr. G. Beyer; Konf. FireResistance in Plastics 2007). Anionic organoclays are organophilieallymodified hydrotalcites based on anion exchange with alkali metalrosinates, unsaturated and saturated fatty acid salts, and sulfonatesand sulfates substituted by long-chain alkyl.

Particularly preferred metal oxides are diantimony trioxide, diantimonytetroxide, diantimony pentoxide or zinc oxide.

Particularly preferred metal hydroxides are aluminum hydroxide (ATH) orgibbsite (hydrargillite), aluminum oxo hydroxide (boehmite) andmagnesium hydroxide (MDH, brucite), and hydromagnesite. In addition togibbsite and boehmite, the other polymorphs of aluminum hydroxidesshould also be mentioned, namely bayerite, nordstrandite and diaspore.

Preferred metal phosphates are metal pyrophosphates. Particularpreference is given to aluminum pyrophosphate and zinc pyrophosphate,and to zinc triphosphate and aluminum triphosphate, and likewise toaluminum metaphosphate and aluminum orthophosphate.

Preferred hydrotalcites are magnesium aluminum hydroxocarbonate andcalcium aluminum hydroxocarbonate.

Among the cationically or anionically modified organoclays, particularpreference is given to the alkyl sulfate- or fatty acidcarboxylate-modified hydrotalcites or long-chain quaternaryammonium-modified clay minerals.

Among the stannate and molybdate salts, particular preference is givento zinc stannate, zinc hydroxy stannate, ammonium heptamolybdate andammonium octamolybdate. Mention should likewise be made of othermolybdates (including polymolybdates) such as calcium zinc molybdate,basic zinc molybdate and calcium molybdate.

Preferred borates are alkali metal and alkaline earth metal borates, andzinc borate. Mention should also be made of aluminum borate, bariumborate, calcium borate, magnesium borate, manganese borate, melamineborate, potassium borate and zinc borophosphate.

Among the metal phosphinates, preference is given to calciumphosphinate, magnesium phosphinate, zinc phosphinate or aluminumphosphinate. Particular preference is given to calciumphenyl(benzene)phosphinate, magnesium phenyl(benzene)phosphinate, zincphenyl(benzene)phosphinate or aluminum phenyl(benzene)phosphinate, andcalcium diethyl(ethane)phosphinate, magnesiumdiethyl(ethane)phosphinate, zinc diethyl(ethane)phosphinate or aluminumdiethyl(ethane)phosphinate.

Among the hypophosphites, particular preference is given to themagnesium, calcium, zinc and aluminum salts.

A further preference of the invention relates to flame retardantcompositions comprising, as component (b), at least one metal-freephosphorus compound.

This at least one metal-free phosphorus compound (b) is red phosphorus,an oligomeric phosphate ester, an oligomeric phosphonate ester, a cyclicphosphonate ester, a thiopyrophosphoric ester, melamine pyrophosphate,melamine polyphosphate, ammonium polyphosphate, melaminiumphenylphosphonate and the monoester salt thereof (WO2010/063 623),melamine benzenephosphinate (WO2010/057851), hydroxyalkylphosphineoxides (WO2009/034023), tetrakis(hydroxymethyl)phosphonium salts andphospholane or phosphole derivatives, and bisphosphoramidates withpiperazine as a bridging member or a phosphonite ester.

Oligomeric phosphate esters are of the formula (IV) or formula (V):

where each R is independently hydrogen, C₁-C₄ alkyl or hydroxyl, n=1 to3 and o is 1 to 10.

Particular preference is given to the oligomer where R_(n)=H andresorcinol or hydroquinone as a constituent of the bridging member, andR_(n)=H and bisphenol A or bisphenol F as a constituent of the bridgingmember.

Oligomeric phosphonate esters are preferably characterized by formula(VI):

-   -   where R³=methyl or phenyl and x is 1 to 20, and R, n are each as        defined above.

Particular preference is given to the oligomer where R₂=H and resorcinolor hydroquinone as a constituent of the bridging member.

Cyclic phosphonate esters preferably have the following formula (VII):

where y=0 or 2. Particular preference is given tobis[5-ethyl-2-methyl-1,3,2-dioxaphosphorinan-5-yl)methyl]methylphosphonate P,P′-dioxide.

Thiopyrophosphoric esters are preferably characterized by the followingformula (VIII):

Particular preference is given to2,2′-oxybis[5,5-dimethyl-1,3,2-dioxaphosphorinane]2,2′-disulfide.

Among the hydroxyalkylphosphine oxides, preference is given toisobutylbis(hydroxymethyl)phosphine oxide and to the combination thereofwith epoxy resins (WO-A 2009/034023).

Among the tetrakis(hydroxyalkyl)phosphonium salts, particular preferenceis given to the tetrakis(hydroxymethyl)phosphonium salts.

Among the phospholane or phosphole derivatives, particular preference isgiven to dihydrophosphole (oxide) derivatives and phospholane (oxide)derivatives, and to the salts thereof (EP 089 296 and EP 1024 166).

Particularly preferred among the bisphosphoramidates are thebis(diorthoxylyl) esters with piperazine as a bridging member.

Among the phosphonite esters, preference is given to phenylbenzenephosphinate and the PH-functionalized derivatives and DOPOderivatives thereof.

DOPO derivatives (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxidederivatives or 6H-dibenzo(c,e)(1,2-oxaphosphorin 6-oxide derivatives(preference being given to PH-functionalized derivatives)) include thecompounds whose structures are as follows (cf. WO-A 2008/119693):

Particular preference is given to:

DOPO may also be replaced by dihydrooxaphosphaanthracen(one) oxide. Anoverview thereof can be found in WO-A 2008/119693.

Further additives (synergists) include: polyols, aminouracils,tris(hydroxyethyl) isocyanurate (THEIC), melamine (iso)cyanurate, POSScompounds and expandable graphite.

Among the polyols, particular preference is given to pentaerythritol,dipentaerythritol and tripentaerythritol.

Among the aminouracils, particular preference is given to1-methyl-6-aminouracil and 1,3-dimethyl-6-aminouracil.

POSS compounds (Polyhedral oligomeric Silsesquioxanes) and derivativesare described in detail in POLYMER, Vol. 46, pp 7855-7866. Preference isgiven here to POSS derivatives based on methylsiloxane.

In addition, it is also possible for tris(hydroxyethyl) isocyanuratepolyterephthalates to be present, and also triazine polymers withpiperazine-1,4-diyl bridging members and morpholin-1-yl end groups.

In addition, the following additives may be present:bisazinpentaerythrityl diphosphate salts, hexaaryloxytriphosphazenes,polyaryloxyphosphazenes and siloxanes (R₂SiO)_(r) or (RSiO_(1.5))_(r).

Metal oxides such as titanium dioxide, silicon dioxide; clay mineralssuch as kaolinite, muscovite, pyrophyllite, bentonite and talc, andother minerals such as wollastonite, quartz, mica, feldspar.

It is also additionally possible for dolomite, bentonite, huntite, orsilicas and the natural or synthetic silicate minerals thereof, to bepresent in the polymer.

Moreover, in addition to the at least one inventive metal phosphate,foam formers may be added to a polymer. Foam formers include: melamine,melamine-formaldehyde resins, urea derivatives such as urea, thiourea,guanamines, benzoguanamine, acetoguanamine and succinylguanamine,dicyandiamide, guanidine and guanidine sulfamate, and other guanidinesalts or allantoins and glycolurils.

Furthermore, a polymer comprising the at least one inventive metalphosphate may also comprise antidripping agents, especially based onpolytetrafluoroethylene. The concentration of such antidripping agentsis 0.01 to 15% by weight based on the polymer to be processed.

In addition, it is also possible to add further components to polymerscomprising the at least one inventive metal phosphate, examples beingfillers and reinforcers such as glass fibers, glass beads or mineraladditives such as chalk. Further additives may be antioxidants, lightstabilizers, lubricants, pigments, nucleating agents and antistats.

The present invention also relates to the use of the inventivetriazine-intercalated metal phosphates with open framework structures asflame retardants in a polymer, paper, textiles or wood plasticcomposites (WPCs).

The inventive flame retardants are very suitable for imparting flameretardancy properties to synthetic, especially thermoplastic, polymers.

A particular embodiment of the invention relates to the use of the atleast one inventive metal phosphate in a polymer as a flame retardant,said polymer being a thermoplastic which is preferably selected from thegroup consisting of polyamide, polycarbonate, polyolefin, polystyrene,polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane,or being a thermoset which is preferably selected from the groupconsisting of epoxy resin (with hardener), phenol resin and melamineresin.

If the polymer in which the at least one inventive metal phosphate isused as a flame retardant is a thermoplastic, preference is given topolyamide, polyurethane, polystyrene, polyolefin or polyester.

If the polymer in which the at least one inventive metal phosphate isused as a flame retardant is a thermoset, preference is given to epoxyresin.

It is also possible to use mixtures of one or more polymers, especiallythermoplastics and/or thermosets, in which the inventive metal phosphateis used as a flame retardant.

Examples of such polymers are:

-   -   1) Polymers of mono- and diolefins, for example polypropylene,        polyisobutylene, polybutene-1, poly-4-methylpentene-1,        polyvinylcyclohexane, polyisoprene or polybutadiene, and        polymers of cycloolefins, for example of cyclopentene or        norbomene and polyethylene (including crosslinked), for example        High Density Polyethylene (HDPE) or High Molecular Weight        (HDPE-HMW), High Density Polyethylene with Ultra-High Molecular        Weight (HDPE-UHMW), Medium Density Polyethylene (MDPE), Low        Density Polyethylene (LDPE) and Linear Low Density Polyethylene        (LLDPE), (VLDPE) and (ULDPE), and copolymers of ethylene and        vinyl acetate.    -   2) Polystyrenes, poly(p-methylstyrene), poly(α-methylstyrene).    -   3) Copolymers and graft copolymers of polybutadiene-styrene or        polybutadiene and (meth)acrylonitrile, for example ABS and MBS.    -   4) Halogenated polymers, for example polychloroprene, polyvinyl        chloride (PVC), polyvinylidene chloride (PVDC), copolymers of        vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate        or vinyl chloride/vinyl acetate.    -   5) Poly(meth)acrylates, polymethyl methacrylates (PMMA),        polyacrylamide and polyacrylonitrile (PAN).    -   6) Polymers of unsaturated alcohols and amines or acyl        derivatives or acetals thereof, for example polyvinyl alcohol        (PYA), polyvinyl acetates, stearates, benzoates or maleates,        polyvinyl butyral, polyallyl phthalates and polyallylmelamines.    -   7) Homo- and copolymers of cyclic ethers, such as polyalkylene        glycols, polyethylene oxides, polypropylene oxides and        copolymers thereof with bisglycidyl ethers.    -   8) Polyacetals such as polyoxymethylenes (POM), and        polyurethane- and acrylate-modified polyacetals.    -   9) Polyphenylene oxides and sulfides, and mixtures thereof with        styrene polymers or polyamides.    -   10) Polyamides and copolyamides derived from diamines and        dicarboxylic acids and/or from aminocarboxylic acids or the        corresponding lactams, for example nylon 4, nylon 6, nylon 6/6,        6/10, 6/9, 6/12, 12/12, nylon 11, nylon 12, aromatic polyamides        derived from m-xylylenediamine and adipic acid, and copolyamides        modified with EPDM or ABS. Examples of polyamides and        copolyamides are derived from ε-caprolactam, adipic acid,        sebacic acid, dodecanoic acid, isophthalic acid, terephthalic        acid, hexamethylenediamine, tetramethylenediamine,        2-methylpentamethylenediamine,        2,2,4-trimethylhexamethylenediamine,        2,4,4-trimethylhexamethylenediamine, m-xylylenediamine or bis (3        -methyl-4-aminocyclohexyl)methane.    -   11) Polyureas, polyimides, polyamideimides, polyetherimides,        polyesterimides, polyhydantoins and polybenzimidazoles.    -   12) Polyesters derived from dicarboxylic acids and dialcohols        and/or hydroxycarboxylic acids or the corresponding lactones,        for example polyethylene terephthalate, polypropylene        terephthalate, polybutylene terephthalate,        poly-1,4-dimethylcyclohexane terephthalate, polyalkylene        naphthalate (PAN) and polyhydroxybenzoates, polylactic esters        and polyglycolic esters.    -   13) Polycarbonates and polyester carbonates.    -   15) Mixtures or alloys of the abovementioned polymers, e.g.,        PP/EPDM, PA/EPDM or ABS, PVC/EVA, PVC/ABS , PBC/MB S , PC/ABS ,        PBTP/ABS , PC/AS , PC/PBT, PVC/CPE, PVC/acrylate,        POM/thermoplastic PU, PC/thermoplastic PU, POM/acrylate,        POM/MBS, PPO/HIPS, PPO/N6,6 and copolymers, PA/HDPE, PA/PP,        PA/PPO, PBT/PC/ABS or PBT/PET/PC, and also TPE-O, TPE-S and        TPE-E;.    -   16) Thermosets such as PF, MF or UF or mixtures thereof.    -   17) Epoxy resins—thermoplastics and thermosets    -   18) Phenol resins.    -   19) Wood-plastic composites (WPC) and polymers based on PEA, PHB        and starch.

The concentration of the at least one triazine-intercalated metalphosphate (a) claimed and component (b) in a polymer or a polymermixture is preferably 0.1 to 60% by weight based on the polymer to beprocessed.

The material thus rendered flame-retardant by addition of the at leastone inventive metal phosphate can be processed to give fibers, films,cast articles, and for treatment of surfaces.

The at least one inventive metal phosphate can also be used for surfacetreatment (impregnation) of fibers, films, textiles or other industrialmaterials.

The present invention further relates to the use of the inventivetriazine-intercalated metal phosphates with open framework structuresfor the production of paints, adhesives, casting resins, coatings,thixotropic agents and flame retardants for polymers.

Accordingly, a further aspect of the present invention is the use of acomposition of the present invention as a flame retardant in a polymer,paper, textile or wood plastic composite (WPC). In particular thepolymer is a thermoplastic, preferably selected from the groupconsisting of polyamide, polycarbonate, polyolefin, polystyrene,polyester, polyvinyl chloride, polyvinyl alcohol, ABS and polyurethane,or is a thermoset, preferably selected from the group consisting ofepoxy resin, phenol resin and melamine resin.

The present invention further relates to the use of the at least oneinventive metal phosphate as a filler in polymers.

A further aspect of the present invention are compounds of the generalformula (I)

(A-H)_(a) ⁽⁺⁾[M_(b) ^(m+)(H₂PO₄)_(x1) ⁽⁻⁾(HPO₄)_(x2) ²⁽⁻⁾(PO₄)_(x3)³⁽⁻⁾(PO₃)_(y) ⁽⁻⁾]^((a−))*pH₂O  (I)

-   -   where    -   (A-H)⁽⁺⁾ is a triazine derivative of the formula (II-1, II-2 or        II-3)

-   -   each M=Al,    -   a is 2,    -   b is 1,    -   m is 3,    -   x₁=0 or 1, x₂=0 or 2, x₃=1 or 0, y=2 or 0 and p is 0 to 5 and        wherein a+mb=x₁+2x₂+3x₃+y.

The present invention further provides a process for preparing theinventive metal phosphate, wherein a substance (A) is reacted with anacidic metal phosphate of the formula H_(a) ⁽⁺⁾[M_(b) ^(m+)(H₂PO₄)_(x1)⁽⁻⁾HPO₄)_(x2) ²⁽⁻⁾(PO₄)_(x3) ³⁽⁻⁾(PO₃)_(y) ⁽⁻⁾]^((a−))* pH₂O.

In particular the present invention relates to a process for preparingthe above mentioned compounds comprising the step of reacting a compound(A), where (A) is a triazine of the formula (II-4), (II-5) or (II-6)

with an acidic metal phosphate of the formula H_(a) ⁽⁺⁾[M_(b)^(m+)(H₂PO₄)_(x1) ⁽⁻⁾HPO₄)_(x2) ²⁽⁻⁾(PO₄)_(x3) ³⁽⁻⁾(PO₃)_(y)⁽⁽⁻⁾]^((a−))* pH₂O where each M=Al.

In a process according to the invention for preparing the inventivemetal phosphate, reaction can take place in water and preferably between20 and 90° C., more preferably between 20 and 60° C. and most preferablybetween 20 and 40° C.

The present invention further provides a compound obtainable by theabove-described process according to the invention.

More particularly, such compounds are notable in that the empiricalcomposition is a melamine aluminum phosphate [(melamine-H)₂⁺[AlP₃O_(10]) ²⁽⁻⁾]_(z), has the following ³¹P MAS NMR shifts (δvalues): −10.6 ppm, −22.0 ppm, −24.5 ppm and -27.6 ppm, and exhibits asingle shift around 40 ppm in the ²⁷Al NMR spectrum. More particularly,the empirical composition is a melamine zinc phosphate [(melamine-H)₂ ⁺[Z_(n)P₂O₇]²⁽⁻⁾]_(z) with the following ³¹P MAS NMR shifts (δ values):+6.2 ppm, +3.7 ppm, +2.0 ppm, −2.5 ppm, −5.5 ppm, −8.2 ppm, −10.7 ppm,−12.1 ppm, −22.2 ppm and −24.7 ppm.

The particular metal phosphate can be prepared, for example, bypremixing in the form of powder and/or granules in a mixer and then byhomogenizing in a polymer melt by compounding (in a twin-screw extruderamong other apparatus). The metal phosphate can possibly also be addeddirectly in the course of processing.

The metal phosphates for the preparation of triazine-intercalated metalphosphates with open framework structures include especially sheetphosphates of the formulae

M(H₂PO₄)₃ and M(H₂PO₄)₂ (M=Al, La, Zn or Mn) or

M(HPO₄)₂*nH₂O or

M(H₂PO₄)(PO₄)*_(n)H₂O (M=Ti, Zr, Sn and Ce) and

condensed phosphates such as triphosphates or pyrophosphates of theformulae H₂AlP₃O₁₀ and

H₂ZnP₂O₇

However, the systems are best prepared via a reaction with melamine as atemplate in aqueous acidic metal salt solution. An alternative processconsists in the reaction of triazine phosphates with aqueous metal saltsolutions (based on Angew. Chem., 1999, 111, 3688-3692).

The metal phosphates with open framework structures thus prepared haveorthophosphate (H_(x)PO₄ type where x=2, 1 or 0), pyrophosphate ortriphosphate as complex ligands, with intercalation of melamine inprotonated form (melamine cation) between the lattice layers or into thecavities and widening of the layer spacings in the case of layerstructures.

In further processing, the inventive triazine-intercalated metalphosphates are incorporated into a suitable polymer matrix. Suitablepolymers which can be used as a substrate are known per se. Forincorporation, preference is given to thermoplastic polymers andthermoset polymer systems, rubbers and textiles.

Melamine is preferred as an intercalate.

With orthophosphate as ligands, the novel intercalates can berepresented by way of example as follows, where (A-H)⁽⁺⁾ (mel-H)⁽⁺⁾(melamine cation):

1. (Mel-H)₂ ⁽⁺⁾[Mn₃ ²⁽⁺⁾(PO₄)₂ ³⁽⁻⁾(PO₃)₂ ⁽⁻⁾(H₂O)₂]²⁽⁻⁾

2. (Mel-H)⁽⁺⁾[Zr⁴⁽⁺⁾(HPO₄)²⁽⁻⁾PO₄)³⁽⁻⁾]⁽⁻⁾

3. (Mel-H)⁽⁺⁾[Zn²⁽⁺⁾(PO₄)³⁽⁻⁾H₂O)₄]⁽⁻⁾

4. (Mel-H)₂ ⁽⁺⁾[Zn²⁽⁺⁾(H₂PO₄)₂ ⁽⁻⁾(HPO₄)²⁽⁻⁾]²⁽⁻⁾

5. (Mel-H)⁽⁺⁾[Zn₂ ²⁽⁺⁾(H₂PO₄)²⁽⁻⁾(PO₄)³]⁽⁻⁾

6. (Mel-H)₂ ⁽⁺⁾[Zn₂ ²⁽⁺⁾(H₂PO₄)²⁽⁻⁾(HPO₄)₂ ²⁽⁻⁾]²⁽⁻⁾

7. (Mel-H)₂ ⁽⁺⁾[Zn₆ ²⁽⁺⁾(HPO₄)²⁽⁻⁾(PO₄)₄ ³⁽⁻⁾]²⁽⁻⁾

8. (Mel-H)₄ ⁽⁺⁾[Zn₆ ²⁽⁺⁾(HPO₄)₂ ²⁽⁻⁾(PO₄)₄ ³⁽⁻⁾]⁴⁽⁻⁾

9. (Mel-H)₂ ⁽⁺⁾[Zn₄ ²⁽⁺⁾(HPO₄)₂ ²⁽⁻⁾(PO₄)₂ ³⁽⁻⁾]²⁽⁻⁾

10. (Mel-H)⁽⁺⁾[Zn₄ ²⁽⁺⁾(PO₄)₃ ³⁽⁻⁾]⁽⁻⁾

11. (Mel-H)₂ ⁽⁺⁾[Zn₂ ²⁽⁺⁾(HPO₄)₃ ²⁽⁻⁾]²⁽⁻⁾

12. (Mel-H)⁽⁺⁾[Zn₂ ²⁽⁺⁾(HPO₄)²⁽⁻⁾(PO₄)³⁽⁻⁾]⁽⁻⁾

13. (Mel-H)⁽⁺⁾[Zn²⁽⁺⁾(H₂PO₄)⁽⁻⁾(HPO₄)²⁽⁻⁾]⁽⁻⁾

14. (Mel-H)₃ ⁽⁺⁾[Al³⁽⁺⁾(PO₄)₂ ³⁽⁻⁾]³⁽⁻⁾

15. (Mel-H)₂ ⁽⁺⁾[Al₅ ³⁽⁺⁾(HPO₄)²⁽⁻⁾(PO₄)₅ ³⁽⁻⁾]²⁽⁻⁾

16. (Mel-H)₂ ⁽⁺⁾[Al₄ ³⁽⁺⁾(HPO₄)²⁽⁻⁾(PO₄)₄ ³⁽⁻⁾]²⁽⁻⁾

17. (Mel-H)⁽⁺⁾[Al³⁽⁺⁾(HPO₄)₂ ²⁽⁻⁾]⁽⁻⁾

18. (Mel-H)⁽⁺⁾[Al³⁽⁺⁾(HPO₄)₂ ²⁽⁻⁾H₂O]⁽⁻⁾

19. (Mel-H)⁽⁺⁾[Al₂ ³⁽⁺⁾Co²⁽⁺⁾(PO₄)₃ ³⁽⁻⁾](−)

20. (Mel-H)⁽⁺⁾[CO²⁽⁺⁾(PO₄)³⁽⁻⁾]⁽⁻⁾

21. (Mel-H)⁽⁺⁾[Sn²⁽⁺⁾(PO₄)³⁽⁻⁾]⁽⁻⁾

22. (Mel-H)₂ ⁽⁺⁾[Zr₂ ⁴⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)⁽⁻⁾]²⁽⁻⁾ (mixed type composed ofortho- and pyrophosphate)

23. (Mel-H)₄ ⁽⁺⁾[Zn₂ ²⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₅ ⁽⁻⁾]⁴⁽⁻⁾ (mixed type composedof metha- and pyrophosphate)

24. (Mel-H)⁽⁺⁾[Zn₂ ²⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₂ ⁽⁻⁾]⁽⁻⁾ (mixed type composed ofmetha- and pyrophosphate)

25. (Mel-H)₂ ⁽⁺⁾[Zn₂ ²⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₃ ⁽⁻⁾]2⁽⁻⁾ (mixed type composedof metha- and pyrophosphate)

26. (Mel-H)₄ ⁽⁺⁾[Zn₁₂ ²⁽⁺⁾(PO₄)₉ ³⁽⁻⁾(PO₃)⁽⁻⁾]⁴⁽⁻⁾ (mixed type composedof ortho- and pyrophosphate)

27. (Mel-H)₄ ⁽⁺⁾[Zn₆ ²⁽⁺⁾(PO₄)₅ ³⁽⁻⁾PO₃)⁽⁻⁾]⁴⁽⁻⁾ (mixed type composed ofortho- and pyrophosphate)

28. (Mel-H)₂ ⁽⁺⁾[Zn₄ ²⁽⁺⁾(PO₄)₃ ³⁽⁻⁾(PO₃)⁽⁻⁾]²⁽⁻⁾ (mixed type composedof ortho- and pyrophosphate)

29. (Mel-H)₄ ⁽⁺⁾[Zn₄ ²⁽⁺⁾(PO₄)₃ ³⁽⁻⁾(PO₃)₃ ⁽⁻⁾]⁴⁽⁻⁾ (pyrophosphate type)

30. (Mel-H)₂ ⁽⁺⁾[Zn₄ ²⁽⁺⁾(PO₄)₃ ³⁽⁻⁾(PO₃)⁽⁻⁾]²⁽⁻⁾ (mixed type composedof ortho- and pyrophosphate)

31. (Mel-H)₂ ⁽⁺⁾[Zn₂ ²⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)³⁽⁻⁾]²⁽⁻⁾ (mixed type composed ofmetha- and pyrophosphate)

32. (Mel-H)₄ ⁽⁺⁾[Al₁₀ ³⁽⁺⁾(PO₄)₁₁ ³⁽⁻⁾PO₃)⁽⁻⁾]⁴⁽⁻⁾ (mixed type composedof ortho- and pyrophosphate)

33. (Mel-H)₄ ⁽⁺⁾[Al₈ ³⁽⁺⁾(PO₄)₉ ³⁽⁻⁾(PO₃)⁽⁻⁾]4⁽⁻⁾ (mixed type composedof ortho- and pyrophosphate)

34. (Mel-H)⁽⁺⁾[Al³⁽⁺⁾(PO₄)³⁽⁻⁾PO₃)⁽⁻⁾]⁽⁻⁾ pyrophosphate type)

35. (Mel-H)₂ ⁽⁺⁾[Al³⁽⁻⁾(H₂PO₄)⁽⁻⁾(HPO₄)₂ ²⁽⁻⁾]²⁽⁻⁾ (pyrophosphate type)

36. (Mel-H)₂ ⁽⁺⁾[Zn²⁽⁺⁾(PO₄)³⁽⁻⁾PO₃)⁽⁻⁾]²⁽⁻⁾ (pyrophosphate type)

37. (Mel-H)₂ ⁽⁺⁾[Al³⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₂ ⁽⁻⁾]²⁽⁻⁾ (triphosphate type) itbeing possible to remove aquo (complexed) water by thermal treatment.

Particular preference is given to 35, 36, 37. Very particular preferenceis given to 36, 37.

The present invention further provides a process for preparing aflame-retardant deformable polymer, wherein the at least one inventivetriazine-intercalated metal phosphate is exfoliated in the polymer.

The invention further provides for the achievement of an anticorrosiveprotective effect by coating of metal surfaces.

FIG. 1 shows, by way of example, a lattice section from an intercalationmodel of melamine in aluminum triphosphate (AIH₂P₃O₁₀) layers (⊕melaminium cation).

The invention is illustrated in detail by examples which follow.

Substances used: melamine (DSM); aluminum tris(dihydrogenphosphate) (50%solution in water) (PRAYON Deutschland), zinc oxide, ortho-phosphoricacid (ALDRICH)

EXAMPLE 1 Synthesis of bismelamine aluminodihydrogenphosphatebis(hydrogen-phosphate)

(Product A)—Precursor Compound

(C₃H₇N₆)₂ ⁽⁺⁾[Al(H₂PO₄)(HPO₄)₂]²⁽⁻⁾

(a=2, M=Al, b=1, m=3, x₁=1, x₂=2, x₃=0, y =0, p =0)

100.9 g (0.8 mol) of melamine are dissolved in 2.4 l of water whilestirring and heating (40 to 60° C.). In this solution, 254.4 g (0.4 mol)of aluminum tris(dihydrogenphosphate) (50% solution in water) are addeddropwise, which forms a thick slurry. This is followed by stirring for30 min, cooling to room temperature, removal of the white precipitateformed by filtration with suction, washing with water and drying toconstant weight at 120° C. Yield: 211.7 g, corresponds to 92.8% oftheory.

Elemental analysis: C: 12.7% (12.6%); H: 3.3% (3.2%); N: 29.9% (29.5%);Al: 4.7% (4.7%); P: 16.4% (16.3%) (theoretical values)

EXAMPLE 2 Synthesis of bismelamine aluminotriphosphate

(Product B) 1

(C₃H₇N₆)₂ ⁽⁺⁾[Al³⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₂ ⁽⁻⁾]²⁽⁻⁾

(a=2, M=Al, b=1, m=3, x₁=0, x₂=0, x₃=1, y=2, p=0)

Product (A) is heated to a virtually constant weight at 280° C. withfrequent mixing for 5 h. The resulting white product has the followingcomposition:

Elemental analysis: C: 13.5% (13.5%); H: 2.6% (2.6%); N: 30.1% (31.5);Al: 5.1% (5.1%); P: 17.5% (17.4%) (theoretical values)

³¹P MAS NMR shifts (6 values): −10.6 ppm, −22.0 ppm, −24.5 ppm and −27.6ppm (see FIG. 2). FIG. 2 here shows the quantitative ³¹P NMR spectrum ofbismelamine aluminotriphosphate (product B) (v_(MAS)=20 KHZ,¹H-decoupled)).

²⁷Al NMR spectrum: sole shift around 40 ppm (see FIG. 4, v_(MAS)=20KHZ).

COMPARATIVE EXAMPLE 3 Synthesis of trismelaminealuminotris(hydrogenphosphate) dihydrate

(Product C)—Precursor Compound

(C₃H₇N₆)3⁽⁺⁾[Al(HPO₄)]₃ ³⁽⁻⁾*2H₂O

(a=3, M=Al, b=1, m=3, x₁=0, x₂=3, x₃=0, y=0, p=2).

94.6 g (0.75 mol) of melamine are dissolved in 2.3 1 of water whilestirring and heating. To this solution are added dropwise 159.0 g (0.25mol) of aluminum tris(dihydrogenphosphate) (50% solution in water),which forms a voluminous slurry. This is followed by stirring for 30minutes, cooling to room temperature, removal of the white precipitateformed by filtration with suction, washing twice with water and dryingto constant weight at 120° C. Yield: 174.0 g, corresponds to 95.0% oftheory.

Elemental analysis: C: 14.8% (14.8%); H: 3.5% (3.9%); N: 33.8% (34.4%)(theoretical values)

EXAMPLE 4 Synthesis of Product B Proceeding from Product C

Preparation of Product C as in Example 3, but with subsequent heattreatment at 210° C. for 5 h. This results in trismelaminealuminotris(dihydrogenphosphate) monohydrate as a precursor.

(C₃H₇N₆)⁽⁺⁾[Al(HPO₄)₃]³⁽⁻⁾*H₂O

Yield: 165.7 g, corresponds to 92.8% of theory.

Elemental analysis: C: 15.1% (15.1%); H: 4.3% (3.7%); N: 35.1% (35.3%);(theoretical values)

Product B is obtained from this precursor by renewed heat treatment at280° C., 6 h, and a decrease in weight of 25% takes place. The result isbismelamine aluminotriphosphate (C3H7N₆)₂ ⁽⁺⁾[Al³⁽⁺⁾(PO₄)³⁽⁻⁾(PO₃)₂⁽⁻⁾]²⁽⁻⁾ (quant, yield)

Elemental analysis: C: 13.4% (13.5%); H: 4.0% (2.6%); N: 29.7% (31.5%);(theoretical values)

It is evident from this that an alternative route to Product B ispossible by use of Product C. However, this process is uneconomic inpractice since about one third of the melamine used has to be removedagain by heat treatment.

If, however, the heat treatment is dispensed with, incorporation intopolyamides, polycarbonates and polyesters is greatly complicated sincesignificant amounts of melamine sublime off. In the case of use ofProduct B prepared according to Example 2, these difficulties, however,do not occur.

EXAMPLE 5 Synthesis of bismelamine zincodiphosphate

(Product D)

(C₃H₇N₆)₂ ⁽⁺⁾[Zn²⁽⁺⁾(PO₄)³⁽⁻⁾PO₃)⁽⁻⁾]²⁽⁻⁾

(a=2, M=Zn, b=1, m=2, x₁=0, x₂=0, x₃=1, y=1, p=0).

Product D obtained by the above method is dried at 280° C. for 5 h, anda decrease in weight of approx. 6.0% takes place.

Elemental analysis: C: 15.1% (14.6%); H: 2.8% (2.9%); N: 34.0% (34.1%);Zn: 12.6% (13.3%); P: 12.2% (12.2%). (theoretical values)

³¹P MAS NMR shifts (δ values): +6.2 ppm, +3.7 ppm, +2.0 ppm, −2.5 ppm,−5.5 ppm, −8.2 ppm, −10.7 ppm, −12.1 ppm, −22.2 ppm and −24.7 ppm. (seeFIG. 3). FIG. 3 here shows the quantitative ³¹P NMR spectrum ofbismelamine zincodiphosphate (Product D) (v_(MAS)=20 KHz).

EXAMPLE 6 Static Thermal Treatment of Precursor Products A and C Theresults are summarized in Tab. 1.

TABLE 1 Thermal treatment of precursor products Product A (%) Product C(%) 100 100 200° C./2 h 94.9 93.9 240° C./2 h 91.4 86.0 280° C./2 h 89.582.4 300° C./2 h 85.9 77.7 300° C./4 h 82.7 76.0

As is clear from Table 1, the inventive Product A is much more thermallystable than the prior art Product C (WO-A 2009/015772). This behaviorwas surprising since it was unforeseeable.

EXAMPLE 7 Static Thermal Treatment of the Heat Treatment Products B, Dand MPP (Melamine Polyphosphate, Prior Art)

The results are summarized in Tab. 2.

TABLE 2 Thermal treatment of heat treatment products Product B (%)Product D (%) Product MPP (%) 100 100 100 200° C./2 h 99.8 99.2 99.1240° C./2 h 99.5 98.9 98.9 280° C./2 h 98.3 97.4 98.0 300° C./2 h 94.394.1 91.3 300° C./4 h 89.7 92.7 83.7

As is evident from Table 2, the inventive Products B and D are much morethermally stable than the prior art MPP. This behavior was surprisingsince it was unforeseeable.

Performance Testing in PYC

I. Production of the Milled Sheet:

The dry mixtures prepared according to Table 1 (R-1, R-2) are eachplasticized in a Collin analytical laboratory roll mill (Model: W100E,manufactured: 2005, from COLLIN) at the temperature specified (rolldiameter: 110 mm, 15 rpm, friction: −15%) for 5 minutes. The films thusobtained (thickness 0.3 mm) are sent to further tests.

II. Conduction of the Static Heat Test (SHT):

Test strips (15 mm×15 mm) are cut out of the milled sheets according toI. These are stressed in a METRASTAT IR 700 test oven (DR. STAPLER GmbH,Dusseldorf) at the temperature specified until significantdiscoloration. Thereafter, the YI (yellowness index) is determined toDIN 53381 with a Spectro-Guide colorimeter (from BYK-GARDNER) andcompared with the YI of the unstressed milled sheet (zero minute value).The results are summarized in tabular form. The smaller the YI at aparticular time, the better the color characteristics.

III. Conduction of Flame Retardancy Testing:

The milled sheets produced above are processed to give pressed slabs(120×100×3 mm) and subjected to a flame retardancy test based on UL94.The UL94 test is described in “Flammability of Plastic Materials forParts in Devices and Appliances”, 5th edition, October, 1996.

IV. Determination of the Mechanical Properties:

The mechanical properties were determined by means of Instron 5569 (5 kNside action grips) to ASTM D412.

V. Conduction of the NMR Measurements:

All measurements were conducted on a Bruker Avance II 200 solid stateMAS spectrometer with a 4.7 T magnet and a double resonance sample headfor 2.5 mm rotors under magic angle spinning conditions (MAS). Therotation frequencies vMAS used are specified for the correspondingmeasurements. Chemical shifts are reported relative to the referencesubstances currently recommended by IUPAC (²⁷Al:1.1 M Al(NO₃)₃ in D₂O;³¹P; 85% phosphoric acid), and the spectrometer calibration wasundertaken with the aid of the standardized shift scale from the protonresonance of TMS.

The following formulations were tested:

EXAMPLE 8 Testing in Flexible PVC

The following dry mixtures are prepared (Table 3)—Starting weights inparts by weight:

TABLE 3 Formulations Components (R-1) (R-2) PVC (Evipol SH 7020) 100 100K value = 70 Plasticizer (DINP)¹) 50 50 Zinc stearate 0.6 0.6Hydrotalcitc²) 2.9 2.9 Antioxidant (bisphenol A) 0.5 0.5 Flame retardant1 (ATH)³) 60 25 Flame retardant 2 (Product B) — 5 Flame retardancyeffect (bum 0/1/1 0/1/1 time in sec. after 3 ignitions) ¹diisononylphthalate, ex BASF ²Sorbacid 911, ex SÜD CHEMIE ³aluminum trihydroxide,APYRAL 40CD, ex NABALTEC

As evident from Table 3, the performance of the inventive formulation(R-2) is comparable to the prior art example (R-1).

TABLE 4 SHT (200° C.) according to II Time [min] (R-1) (R-2) 3 10.3 5.86 10.0 5.5 9 11.0 5.7 12 11.5 6.4 15 12.9 7.4 18 13.9 8.6 21 15.5 10.324 18.8 12.7 27 22.0 15.8 30 25.8 19.3 33 31.7 24.9 36 40.3 33.3 39 52.944.5 42 70.5 62.7 45 95.3 76.7 48 110.8 85.5 51 117.2 89.2 54 118.4 90.957 117.6 91.3 60 115.72 92.4

As evident from Table 4, the inventive formulation (R-2) hassignificantly better color characteristics, especially in relation tothe initial color, than the noninventive formulation (R-1)

TABLE 5 Mechanical properties Tensile strength Breaking strain Young'smodulus [MPa] [%] [MPa] (R-1) 13.64 331.38 33.59 (R-2) 15.24 368.4525.27

Table 5 shows that the mechanical properties of the inventiveformulation (R-2) are actually improved compared to the prior art (R-1).

1-26. (canceled)
 27. A compound of the general formula (I):(A-H)_(a) ⁽⁺⁾[M_(b) ^(m+)(H₂PO₄)_(x1) ⁽⁻⁾(HPO₄)_(x2) ²⁽⁻⁾(PO₄)_(x3)³⁽⁻⁾(PO₃)_(y) ⁽⁻⁾]^((a−))*pH₂O  (I) wherein (A-H)⁽⁺⁾ is a triazinederivative of the formula (II-1, II-2 or II-3)

wherein each M is independently selected from Cu, Mg, Ca, Zn, Mn, Fe,Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La, Ti, Zr, Ce, or Sn; a is 1 to 6,b is 1 to 14, m is 1 to 4, x₁, x₂, x₃, and y independently are 0 to 12,wherein at least one of the variables x₁, x₂, and x₃ is >0, and p is 0to 5, wherein a+mb=x₁+2x₂+3x₃+y, wherein the following compounds areexcluded[(A-H)⁺]_(c)[M^(c+)(HPO₄ ²⁻),], and  (III-1)[(A-H)⁺]_(c)[M^(c+)(P₂O₇ ⁴⁻)_(c/2)],  (III-2) wherein M is Ca, Mg, Zn,or Al, and c is the oxidation number of the metal.
 28. The compound ofclaim 27, wherein x₁ is 1, x₂ is 2, x₃ is 0, and y is
 0. 29. Thecompound of claim 28, wherein p is
 0. 30. The compound of claim 27,wherein M is Al, Zn, Mg, or Ca.
 31. The compound of claim 30, wherein x₁is 1, x₂ is 2, x₃ is 0, and y is
 0. 32. The compound of claim 31,wherein p is
 0. 33. The compound of claim 30, wherein x₁ is 0, x₂ is 0,x₃ is 1, and y is
 2. 34. The compound of claim 33, wherein p is
 0. 35.The compound of claim 27, wherein (A-H)⁽⁺⁾ is melamine (II-1), a is 2, Mis Al, b is 1, m is 3, x₁ is 1, x₂ is 2, x₃ is 0, y is 0, p is 0, andthe compound has the following formula:(Mel-H)₂ ⁽⁺⁾[Al³⁽⁺⁾(H₂PO₄)⁽⁻⁾(HPO₄)₂ ²⁽⁻⁾]²⁽⁻⁾.
 36. The compound ofclaim 27, wherein x₁ is 0, x₂ is 0, x₃ is 1, and y is
 2. 37. Thecompound of claim 36, wherein p is
 0. 38. The compound of claim 27,wherein (A-H)⁽⁺⁾ is melamine (II-1), a is 2, M is Al, b is 1, m is 3, x₁is 0, x₂ is 0, x₃ is 1, y is 2, p is 0, and the compound has thefollowing formula:(Mel-H)₂ ⁽⁺⁾[Al³⁽⁺⁾(H₂PO₄)⁽⁻⁾(PO₃)₂ ²⁽⁻⁾]²⁽⁻⁾.
 39. A compositioncomprising a compound of claim 27 and a polymer matrix.
 40. Thecomposition of claim 39, wherein the compound of claim 27 is exfoliatedin the polymer matrix, and the composition is a flame-retardantdeformable polymer.
 41. The composition of claim 39, wherein the polymermatrix comprises a thermoplastic polymer, a thermoset polymer, a rubber,a textile, or a combination thereof.
 42. A process for preparing acompound according to claim 27, the process comprising: reacting acompound (A), wherein the compound (A) is a triazine of the formula(II-4), (II-5), or (II-6)

with an acidic metal phosphate of the formulaH_(a) ⁽⁺⁾[M_(b) ^(m+)(H₂PO₄)_(x1) ⁽⁻⁾(HPO₄)_(x2) ²⁽⁻⁾(PO₄)_(x3)³⁽⁻⁾(PO₃)_(y) ⁽⁻⁾]^((a−))*pH₂O, wherein each M is independently selectedfrom Cu, Mg, Ca, Zn, Mn, Fe, Co, Ni, TiO, ZrO, VO, B, Si, Al, Sb, La,Ti, Zr, Ce, or Sn; a is 1 to 6, b is 1 to 14, m is 1 to 4, x₁, x₂, x₃,and y independently are 0 to 12, wherein at least one of the variablesx₁, x₂, and x₃ is greater than 0, and p is 0 to 5, whereina+mb=x₁+2x₂+3x₃ +y.
 43. The process of claim 42, wherein the reactingtakes place in water at a temperature between 20° C. and 90° C.
 44. Theprocess of claim 43, wherein the temperature is between 20° C. and 60°C.
 45. The process of claim 43, wherein the temperature is between 20°C. and 40° C.
 46. A compound obtainable by the process according toclaim 42.